JPWO2020004243A1 - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- JPWO2020004243A1 JPWO2020004243A1 JP2020527469A JP2020527469A JPWO2020004243A1 JP WO2020004243 A1 JPWO2020004243 A1 JP WO2020004243A1 JP 2020527469 A JP2020527469 A JP 2020527469A JP 2020527469 A JP2020527469 A JP 2020527469A JP WO2020004243 A1 JPWO2020004243 A1 JP WO2020004243A1
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- liquid diene
- diene rubber
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 78
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 35
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 12
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 abstract description 15
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 25
- -1 boron carbides Chemical class 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 150000001993 dienes Chemical class 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 11
- 235000019241 carbon black Nutrition 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000002897 diene group Chemical group 0.000 description 7
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006232 furnace black Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000357292 Monodactylus Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Chemical class O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical class OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- ZTJHDEXGCKAXRZ-FNORWQNLSA-N (3e)-octa-1,3,7-triene Chemical compound C=CCC\C=C\C=C ZTJHDEXGCKAXRZ-FNORWQNLSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- JHTICDZLXFNVKL-UHFFFAOYSA-N 1-ethenyl-4-(4-phenylbutyl)benzene Chemical compound C1=CC(C=C)=CC=C1CCCCC1=CC=CC=C1 JHTICDZLXFNVKL-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DXFURPHVJQITAC-UHFFFAOYSA-N 4-benzyl-1-ethenyl-2-ethylbenzene Chemical compound C1=C(C=C)C(CC)=CC(CC=2C=CC=CC=2)=C1 DXFURPHVJQITAC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/10—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
- C08L2207/324—Liquid component is low molecular weight polymer
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Abstract
過酸化物架橋系の水素添加ニトリルゴムを含む組成物において、その組成物の架橋物が有する優れた特性を損なうことなく、スコーチ安定性を向上したゴム組成物及びその架橋物を提供する。水素添加ニトリルゴム（Ａ）１００質量部、フィラー（Ｂ）５〜１００質量部、有機過酸化物（Ｃ）１〜１０質量部、及びゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定されたポリスチレン換算の重量平均分子量が３，０００〜１２０，０００である液状ジエン系ゴム（Ｄ）１〜２０質量部を含むゴム組成物。Provided are a rubber composition having improved scorch stability and a crosslinked product thereof without impairing the excellent properties of the crosslinked product of the composition in a composition containing a hydrogenated nitrile rubber of a peroxide cross-linking system. 100 parts by mass of hydrogenated nitrile rubber (A), 5 to 100 parts by mass of filler (B), 1 to 10 parts by mass of organic peroxide (C), and polystyrene equivalent measured by gel permeation chromatography (GPC). A rubber composition containing 1 to 20 parts by mass of a liquid diene rubber (D) having a weight average molecular weight of 3,000 to 120,000.
Description
本発明はゴム組成物に関する。 The present invention relates to rubber compositions.
従来から、水素添加ニトリルゴムは、耐薬品性、耐熱性に優れるゴムとして知られており、ガスケット、Ｏ−リング、オイルシール、ホース、ベルトなど種々の用途に用いられてきている。この水素添加ニトリルゴムを含む組成物及びこれから得られる架橋物の物性の改良を目的に、水素添加ニトリルゴム及び低分子量の液状ジエン系ゴムを含む組成物の検討がされている。 Conventionally, hydrogenated nitrile rubber has been known as a rubber having excellent chemical resistance and heat resistance, and has been used for various purposes such as gaskets, O-rings, oil seals, hoses, and belts. For the purpose of improving the physical properties of the composition containing the hydrogenated nitrile rubber and the crosslinked product obtained from the composition, a composition containing the hydrogenated nitrile rubber and a low molecular weight liquid diene rubber has been studied.
例えば、特許文献１では、ゴム組成物のロール加工性を改善することを目的に、水添ニトリルゴム、及び低分子量（平均分子量：１０００〜３０００程度）の液状ポリブタジエンを含む組成物が検討されている。また、特許文献２では、耐発泡性、フェノール系接着剤を塗布した金属部材との接着性向上を目的とし、ヨウ素価が低いニトリルゴムと、ビニル化度が高く低分子量（平均分子量：１０００〜３０００程度）の液状ポリブタジエンを含む組成物が検討されている。 For example, in Patent Document 1, a composition containing hydrogenated nitrile rubber and low molecular weight (average molecular weight: about 1000 to 3000) liquid polybutadiene is studied for the purpose of improving the roll processability of the rubber composition. There is. Further, in Patent Document 2, for the purpose of improving foam resistance and adhesiveness to a metal member coated with a phenol-based adhesive, nitrile rubber having a low iodine value and a low molecular weight (average molecular weight: 1000 to) having a high degree of vinylization are used. A composition containing liquid polybutadiene (about 3000) has been studied.
水素添加ニトリルゴムを含む組成物から得られる架橋物は、耐薬品性、耐熱性に優れる材料である。しかし、過酸化物架橋を行い得る水素添加ニトリルゴムを含む組成物において、その組成物から得られる架橋物が有する優れた特性を損なうことなく、スコーチ安定性を向上する方法は知られていない。 The crosslinked product obtained from the composition containing hydrogenated nitrile rubber is a material having excellent chemical resistance and heat resistance. However, in a composition containing a hydrogenated nitrile rubber capable of performing peroxide cross-linking, there is no known method for improving scorch stability without impairing the excellent properties of the cross-linked product obtained from the composition.
本発明は、上記の実情に鑑みてなされたものであり、過酸化物架橋系の水素添加ニトリルゴムを含む組成物において、その組成物の架橋物が有する優れた特性を損なうことなく、スコーチ安定性を向上したゴム組成物及びその架橋物を提供する。 The present invention has been made in view of the above circumstances, and in a composition containing a peroxide-crosslinked hydrogenated nitrile rubber, the scorch is stable without impairing the excellent properties of the crosslinked product of the composition. Provided are a rubber composition having improved properties and a crosslinked product thereof.
本発明者らが検討を行った結果、水素添加ニトリルゴム、フィラー、有機過酸化物、特定の分子量を有する液状ジエン系ゴムを特定の配合比で含むゴム組成物は、水素添加ニトリルゴムの架橋物が有する優れた特性を損なうことなく、スコーチ安定性を向上できることを見い出し、本発明を完成するに至った。 As a result of studies by the present inventors, a rubber composition containing a hydrogenated nitrile rubber, a filler, an organic peroxide, and a liquid diene rubber having a specific molecular weight in a specific compounding ratio is obtained by cross-linking the hydrogenated nitrile rubber. We have found that scorch stability can be improved without impairing the excellent properties of the object, and have completed the present invention.
すなわち、本発明は以下〔１〕〜〔３〕に関する。
〔１〕 水素添加ニトリルゴム（Ａ）１００質量部、フィラー（Ｂ）５〜１００質量部、有機過酸化物（Ｃ）１〜１０質量部、及びゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定されたポリスチレン換算の重量平均分子量が３，０００〜１２０，０００である液状ジエン系ゴム（Ｄ）１〜２０質量部を含むゴム組成物。
〔２〕 液状ジエン系ゴム（Ｄ）のビニル結合量が７０モル％以下である〔１〕に記載のゴム組成物。
〔３〕 〔１〕又は〔２〕に記載のゴム組成物の架橋物。That is, the present invention relates to the following [1] to [3].
[1] Measured by 100 parts by mass of hydrogenated nitrile rubber (A), 5 to 100 parts by mass of filler (B), 1 to 10 parts by mass of organic peroxide (C), and gel permeation chromatography (GPC). A rubber composition containing 1 to 20 parts by mass of a liquid diene rubber (D) having a polystyrene-equivalent weight average molecular weight of 3,000 to 120,000.
[2] The rubber composition according to [1], wherein the liquid diene rubber (D) has a vinyl bond amount of 70 mol% or less.
[3] A crosslinked product of the rubber composition according to [1] or [2].
本発明によれば、スコーチ安定性が向上した水素添加ニトリルゴムを含むゴム組成物が得られ、そのゴム組成物から得られる架橋物は、水素添加ニトリルゴムの架橋物が有する優れた特性が損なわれることがない。 According to the present invention, a rubber composition containing a hydrogenated nitrile rubber having improved scorch stability can be obtained, and the crosslinked product obtained from the rubber composition impairs the excellent properties of the crosslinked product of the hydrogenated nitrile rubber. There is no rubber.
［水素添加ニトリルゴム（Ａ）］
本発明のゴム組成物で用いる水素添加ニトリルゴム（Ａ）とは、アクリロニトリル−ブタジエン共重合ゴムを水素添加して得られたものであり、２０℃において固形状で取り扱うことができるゴムをいい、水素添加ニトリルゴム（Ａ）の１００℃におけるムーニー粘度ＭＬ1+4は通常２０〜２００の範囲にあり、５５〜１００の範囲にあることが好ましく、６５〜９５の範囲にあることがより好ましい。[Hydrogenated nitrile rubber (A)]
The hydrogenated nitrile rubber (A) used in the rubber composition of the present invention is obtained by hydrogenating acrylonitrile-butadiene copolymer rubber, and refers to a rubber that can be handled in a solid state at 20 ° C. The Mooney viscosity ML 1 + 4 of the hydrogenated nitrile rubber (A) at 100 ° C. is usually in the range of 20 to 200, preferably in the range of 55 to 100, and more preferably in the range of 65 to 95.
水素添加ニトリルゴム（Ａ）のヨウ素価は３〜５０（ｍｇ／１００ｍｇ）であることが好ましく、５〜４０（ｍｇ／１００ｍｇ）であることがより好ましい。
水素添加ニトリルゴムのアクリロニトリル単位の含有量は、１５〜６０質量％であることが好ましく、３０〜５５質量％であることがより好ましい。The iodine value of the hydrogenated nitrile rubber (A) is preferably 3 to 50 (mg / 100 mg), more preferably 5 to 40 (mg / 100 mg).
The content of the acrylonitrile unit of the hydrogenated nitrile rubber is preferably 15 to 60% by mass, more preferably 30 to 55% by mass.
［フィラー（Ｂ）］
本発明のゴム組成物で用いるフィラー（Ｂ）としては、例えば、カーボンブラック、シリカ、クレー、マイカ、炭酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、硫酸バリウム、酸化チタン、ガラス繊維、繊維状フィラー、ガラスバルーン等の無機フィラー；樹脂粒子、木粉、及びコルク粉等の有機フィラーなどが挙げられる。このようなフィラーがゴム組成物に含まれることにより、機械強度、耐熱性、又は耐候性等の物性の改善、硬度の調整、ゴムの増量をすることができる。[Filler (B)]
Examples of the filler (B) used in the rubber composition of the present invention include carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, and fibrous filler. Inorganic fillers such as glass balloons; organic fillers such as resin particles, wood powder, and cork powder can be mentioned. By including such a filler in the rubber composition, it is possible to improve physical properties such as mechanical strength, heat resistance, or weather resistance, adjust the hardness, and increase the amount of rubber.
機械強度の向上等の物性の改善などの観点からは、上記フィラー（Ｂ）の中でも、カーボンブラック及びシリカが好ましい。
上記カーボンブラックとしては、例えば、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック、及びケッチェンブラックなどが挙げられる。架橋速度や機械強度向上の観点からは、これらカーボンブラックの中でも、ファーネスブラックが好ましい。これらカーボンブラックは、１種単独で用いてもよく、２種以上を併用してもよい。Among the fillers (B), carbon black and silica are preferable from the viewpoint of improving physical properties such as improvement of mechanical strength.
Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and Ketjen black. Among these carbon blacks, furnace black is preferable from the viewpoint of improving the cross-linking speed and mechanical strength. These carbon blacks may be used alone or in combination of two or more.
前記カーボンブラックの平均粒径としては、分散性、機械強度、硬度などを向上させる観点から５〜１００ｎｍが好ましく、５〜８０ｎｍがより好ましく、５〜７０ｎｍがさらに好ましい。 The average particle size of the carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, and even more preferably 5 to 70 nm from the viewpoint of improving dispersibility, mechanical strength, hardness and the like.
なお、カーボンブラックの平均粒径は、透過型電子顕微鏡により粒子の直径を測定してその平均値を算出することにより求めることができる。
上記ファーネスブラックの市販品としては、例えば、三菱化学株式会社「ダイヤブラック」、東海カーボン株式会社製「シースト」などが挙げられる。アセチレンブラックの市販品としては、例えば、電気化学工業株式会社製「デンカブラック」などが挙げられる。ケッチェンブラックの市販品としては、例えば、ライオン株式会社製「ＥＣＰ６００ＪＤ」などが挙げられる。The average particle size of carbon black can be obtained by measuring the diameter of the particles with a transmission electron microscope and calculating the average value.
Examples of commercially available products of the furnace black include "Dia Black" manufactured by Mitsubishi Chemical Corporation and "Seast" manufactured by Tokai Carbon Corporation. Examples of commercially available products of acetylene black include "Denka Black" manufactured by Denki Kagaku Kogyo Co., Ltd. Examples of commercially available products of Ketjen Black include "ECP600JD" manufactured by Lion Corporation.
上記カーボンブラックは、水素添加ニトリルゴム（Ａ）への濡れ性、分散性などを向上させる観点から、硝酸、硫酸、塩酸又はこれらの混合酸等による酸処理や、空気存在下での熱処理による表面酸化処理を行ってもよい。また、本発明のゴム組成物及びこの組成物から得られる架橋物の機械強度向上の観点から、黒鉛化触媒の存在下に２，０００〜３，０００℃で熱処理を行ってもよい。なお、黒鉛化触媒としては、ホウ素、ホウ素酸化物（例えば、Ｂ2Ｏ2、Ｂ2Ｏ3、Ｂ4Ｏ3、Ｂ4Ｏ5等）、ホウ素オキソ酸（例えば、オルトホウ酸、メタホウ酸、四ホウ酸等）及びその塩、ホウ素炭化物（例えば、Ｂ4Ｃ、Ｂ6Ｃ等）、窒化ホウ素（ＢＮ）、その他のホウ素化合物が好適に用いられる。From the viewpoint of improving the wettability and dispersibility of the hydrogenated nitrile rubber (A), the carbon black has a surface obtained by acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof, or heat treatment in the presence of air. Oxidation treatment may be performed. Further, from the viewpoint of improving the mechanical strength of the rubber composition of the present invention and the crosslinked product obtained from the composition, heat treatment may be performed at 2,000 to 3,000 ° C. in the presence of a graphitizing catalyst. Examples of the graphitization catalyst include boron, boron oxide (for example, B 2 O 2 , B 2 O 3 , B 4 O 3 , B 4 O 5, etc.), and boron oxo acid (for example, orthoboric acid, metaboric acid, etc.). (Terabolic acid, etc.) and salts thereof, boron carbides (for example, B 4 C, B 6 C, etc.), boron nitride (BN), and other boron compounds are preferably used.
上記カーボンブラックは、粉砕等により粒度を調整した後、用いることもできる。カーボンブラックの粉砕には、高速回転粉砕機（ハンマーミル、ピンミル、ケージミル）や各種ボールミル（転動ミル、振動ミル、遊星ミル）、撹拌ミル（ビーズミル、アトライター、流通管型ミル、アニュラーミル）等が使用できる。 The carbon black can also be used after adjusting the particle size by pulverization or the like. For crushing carbon black, high-speed rotary crushers (hammer mills, pin mills, cage mills), various ball mills (rolling mills, vibration mills, planetary mills), stirring mills (bead mills, attritors, distribution tube mills, annual mills) Etc. can be used.
上記シリカとしては、湿式シリカ(含水ケイ酸)、乾式シリカ(無水ケイ酸)、ケイ酸カルシウム、ケイ酸アルミニウム等を挙げることができる。これらシリカの中でも、加工性及び機械強度を一層向上させる観点から、湿式シリカが好ましい。これらシリカは、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of the silica include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate and the like. Among these silicas, wet silica is preferable from the viewpoint of further improving workability and mechanical strength. These silicas may be used alone or in combination of two or more.
シリカの平均粒径は、加工性及び機械強度を向上する観点から、０．５〜２００ｎｍが好ましく、５〜１５０ｎｍがより好ましく、１０〜１００ｎｍがさらに好ましい。
なお、シリカの平均粒径は、透過型電子顕微鏡により粒子の直径を測定して、その平均値を算出することにより求めることができる。The average particle size of silica is preferably 0.5 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 100 nm from the viewpoint of improving processability and mechanical strength.
The average particle size of silica can be obtained by measuring the diameter of the particles with a transmission electron microscope and calculating the average value thereof.
本発明のゴム組成物において、水素添加ニトリルゴム（Ａ）１００質量部に対するフィラー（Ｂ）の含有量は５〜１００質量部であり、１０〜９０質量部が好ましく、２０〜６０質量部がより好ましい。フィラー（Ｂ）の含有量が前記範囲内であると、ゴム組成物の加工性、スコーチ安定性が向上する。 In the rubber composition of the present invention, the content of the filler (B) with respect to 100 parts by mass of the hydrogenated nitrile rubber (A) is 5 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass. preferable. When the content of the filler (B) is within the above range, the processability and scorch stability of the rubber composition are improved.
［有機過酸化物（Ｃ）］
本発明で用いる有機過酸化物（Ｃ）は、本発明のゴム組成物のゴム成分を架橋し得る成分である。有機過酸化物（Ｃ）としては、例えば、シクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、及び１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼンなどが挙げられる。[Organic peroxide (C)]
The organic peroxide (C) used in the present invention is a component capable of cross-linking the rubber component of the rubber composition of the present invention. Examples of the organic peroxide (C) include cyclohexanone peroxide, methylacetate acetate peroxide, t-butylperoxyisobutyrate, t-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, and dicumyl peroxide. , Di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene and the like.
これら有機過酸化物（Ｃ）は１種単独で用いてもよく、２種以上を併用してもよい。上記有機過酸化物（Ｃ）の含有量は、水素添加ニトリルゴム（Ａ）１００質量部に対し、１〜１０質量部である。この範囲で有機過酸化物（Ｃ）を含むことにより、得られる架橋物の力学物性に優れる。力学物性により優れる架橋物を得る観点から、有機過酸化物（Ｃ）の含有量は、水素添加ニトリルゴム（Ａ）１００質量部に対し、１〜８質量部であることが好ましく、２〜５質量部であることがより好ましい。 These organic peroxides (C) may be used alone or in combination of two or more. The content of the organic peroxide (C) is 1 to 10 parts by mass with respect to 100 parts by mass of the hydrogenated nitrile rubber (A). By containing the organic peroxide (C) in this range, the mechanical properties of the obtained crosslinked product are excellent. From the viewpoint of obtaining a crosslinked product having more excellent mechanical properties, the content of the organic peroxide (C) is preferably 1 to 8 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of the hydrogenated nitrile rubber (A). More preferably, it is by mass.
［液状ジエン系ゴム（Ｄ）］
本発明で用いる液状ジエン系ゴム（Ｄ）とは、液状の重合体でありその重合体を構成する単量体単位として共役ジエン単位を含む。共役ジエンとしては、例えば、ブタジエン、イソプレン；２，３−ジメチルブタジエン、２−フェニルブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、１，３−オクタジエン、１，３−シクロヘキサジエン、２−メチル−１，３−オクタジエン、１，３，７−オクタトリエン、ミルセン、及びクロロプレン等のブタジエン及びイソプレン以外の共役ジエン（ｄ１）が挙げられる。液状ジエン系ゴム（Ｄ）に含まれる共役ジエン単位としては、イソプレン及び／又はブタジエンの単量体単位が含まれていることが好ましい。[Liquid diene rubber (D)]
The liquid diene rubber (D) used in the present invention is a liquid polymer and contains a conjugated diene unit as a monomer unit constituting the polymer. Examples of the conjugated diene include butadiene and isoprene; 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-octadien. , 1,3-Cyclohexadiene, 2-methyl-1,3-octadene, 1,3,7-octatriene, myrsen, and conjugated diene (d1) other than butadiene and isoprene such as chloroprene. The conjugated diene unit contained in the liquid diene rubber (D) preferably contains a monomer unit of isoprene and / or butadiene.
液状ジエン系ゴム（Ｄ）は、その重合体を構成する全単量体単位のうち、５０質量％以上がイソプレン及び／又はブタジエンの単量体単位であることが好ましい一態様である。イソプレン単位及びブタジエン単位の合計含有量は、液状ジエン系ゴム（Ｄ）の全単量体単位に対して６０〜１００質量％であることが好ましく、７０〜１００質量％であることがより好ましく、１００質量％であることがさらに好ましい。 The liquid diene rubber (D) is preferably one embodiment in which 50% by mass or more of all the monomer units constituting the polymer are isoprene and / or butadiene monomer units. The total content of the isoprene unit and the butadiene unit is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, based on all the monomer units of the liquid diene rubber (D). It is more preferably 100% by mass.
上記液状ジエン系ゴム（Ｄ）に含まれ得るイソプレン単位及びブタジエン単位以外の他の単量体単位としては、前述したイソプレン及びブタジエン以外の共役ジエン（ｄ１）単位、芳香族ビニル化合物（ｄ２）単位などが挙げられる。 Examples of the monomer unit other than the isoprene unit and the butadiene unit that can be contained in the liquid diene rubber (D) include the conjugated diene (d1) unit and the aromatic vinyl compound (d2) unit other than the isoprene and butadiene described above. And so on.
芳香族ビニル化合物（ｄ２）としては、例えば、スチレン、α−メチルスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、４−プロピルスチレン、４−ｔ−ブチルスチレン、４−シクロヘキシルスチレン、４−ドデシルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、２，４，６−トリメチルスチレン、２−エチル−４−ベンジルスチレン、４−（フェニルブチル）スチレン、１−ビニルナフタレン、２−ビニルナフタレン、ビニルアントラセン、Ｎ，Ｎ−ジエチル−４−アミノエチルスチレン、ビニルピリジン、４−メトキシスチレン、モノクロロスチレン、ジクロロスチレン、及びジビニルベンゼンなどが挙げられる。これら芳香族ビニル化合物の中では、スチレン、α−メチルスチレン、及び４−メチルスチレンが好ましい。 Examples of the aromatic vinyl compound (d2) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, and 4-cyclohexylstyrene. , 4-Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene , 2-Vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like. Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferable.
上記液状ジエン系ゴム（Ｄ）における、ブタジエン単位及びイソプレン単位以外の他の単量体単位の含有量は、５０質量％以下であり、４５質量％以下がより好ましく、４０質量％以下がさらに好ましい。例えば、芳香族ビニル化合物（ｄ２）単位が上記範囲以下であると、ゴム組成物の加工性が向上する傾向にある。 The content of the monomer unit other than the butadiene unit and the isoprene unit in the liquid diene rubber (D) is 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. .. For example, when the unit of the aromatic vinyl compound (d2) is not more than the above range, the processability of the rubber composition tends to be improved.
液状ジエン系ゴム（Ｄ）としては、共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体を、例えば、乳化重合法、又は溶液重合法等により重合して得られる重合体が好ましい。 The liquid diene-based rubber (D) includes a polymer obtained by polymerizing a conjugated diene and other monomers other than the conjugated diene contained as necessary by, for example, an emulsion polymerization method or a solution polymerization method. preferable.
上記乳化重合法としては、公知又は公知に準ずる方法を適用できる。例えば、所定量の共役ジエンを含む単量体を乳化剤の存在下に乳化分散し、ラジカル重合開始剤により乳化重合する。 As the emulsification polymerization method, a known or known method can be applied. For example, a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is carried out with a radical polymerization initiator.
乳化剤としては、例えば炭素数１０以上の長鎖脂肪酸塩及びロジン酸塩などが挙げられる。長鎖脂肪酸塩としては、例えば、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸等の脂肪酸のカリウム塩又はナトリウム塩などが挙げられる。 Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin salts. Examples of the long-chain fatty acid salt include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.
分散剤としては通常、水が使用され、重合時の安定性が阻害されない範囲で、メタノール、エタノールなどの水溶性有機溶媒を含んでいてもよい。
ラジカル重合開始剤としては、例えば過硫酸アンモニウムや過硫酸カリウムのような過硫酸塩、有機過酸化物、過酸化水素等が挙げられる。Water is usually used as the dispersant, and a water-soluble organic solvent such as methanol or ethanol may be contained as long as the stability during polymerization is not impaired.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
得られる液状ジエン系ゴム（Ｄ）の分子量を調整するため、連鎖移動剤を使用してもよい。連鎖移動剤としては、例えば、ｔ−ドデシルメルカプタン、ｎ−ドデシルメルカプタン等のメルカプタン類；四塩化炭素、チオグリコール酸、ジテルペン、ターピノーレン、γ−テルピネン、α−メチルスチレンダイマーなどが挙げられる。 A chain transfer agent may be used to adjust the molecular weight of the obtained liquid diene rubber (D). Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, γ-terpinene, α-methylstyrene dimer and the like.
乳化重合の温度は、使用するラジカル重合開始剤の種類などにより適宜設定できるが、通常０〜１００℃の範囲、好ましくは０〜６０℃の範囲である。重合様式は、連続重合、回分重合のいずれでもよい。 The temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used and the like, but is usually in the range of 0 to 100 ° C, preferably in the range of 0 to 60 ° C. The polymerization mode may be either continuous polymerization or batch polymerization.
重合反応は、重合停止剤の添加により停止できる。重合停止剤としては、例えば、イソプロピルヒドロキシルアミン、ジエチルヒドロキシルアミン、ヒドロキシルアミン等のアミン化合物、ヒドロキノンやベンゾキノン等のキノン系化合物、亜硝酸ナトリウム等が挙げられる。 The polymerization reaction can be stopped by adding a polymerization inhibitor. Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
重合反応停止後、必要に応じて老化防止剤を添加してもよい。重合反応停止後、得られたラテックスから必要に応じて未反応単量体を除去し、次いで、塩化ナトリウム、塩化カルシウム、塩化カリウム等の塩を凝固剤とし、必要に応じて硝酸、硫酸等の酸を添加して凝固系のｐＨを所定の値に調整しながら、上記液状ジエン系ゴム（Ｄ）を凝固させた後、分散溶媒を分離することによって重合体を回収する。次いで水洗、及び脱水後、乾燥することで、上記液状ジエン系ゴム（Ｄ）が得られる。なお、凝固の際に、必要に応じて予めラテックスと乳化分散液にした伸展油とを混合し、油展した液状ジエン系ゴム（Ｄ）として回収してもよい。 After the polymerization reaction is stopped, an anti-aging agent may be added if necessary. After terminating the polymerization reaction, unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and if necessary, nitrates, sulfuric acid and the like are added. After coagulating the liquid diene rubber (D) while adjusting the pH of the coagulation system to a predetermined value by adding an acid, the polymer is recovered by separating the dispersion solvent. Then, the liquid diene rubber (D) is obtained by washing with water, dehydrating, and then drying. At the time of solidification, if necessary, latex and a spreading oil prepared as an emulsified dispersion may be mixed and recovered as an oil-expanded liquid diene-based rubber (D).
上記溶液重合法としては、公知又は公知に準ずる方法を適用できる。例えば、溶媒中で、チーグラー系触媒、メタロセン系触媒、アニオン重合可能な活性金属又は活性金属化合物を使用して、必要に応じて極性化合物の存在下で、共役ジエンを含む単量体を重合する。 As the solution polymerization method, a known or known method can be applied. For example, in a solvent, a Cheegler-based catalyst, a metallocene-based catalyst, an anionically polymerizable active metal or an active metal compound is used to polymerize a monomer containing a conjugated diene, if necessary, in the presence of a polar compound. ..
溶媒としては、例えば、ｎ−ブタン、ｎ−ペンタン、イソペンタン、ｎ−ヘキサン、ｎ−ヘプタン、イソオクタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環式炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などが挙げられる。 Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.
アニオン重合可能な活性金属としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属；ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等のアルカリ土類金属；ランタン、ネオジム等のランタノイド系希土類金属等が挙げられる。アニオン重合可能な活性金属の中でもアルカリ金属及びアルカリ土類金属が好ましく、アルカリ金属がより好ましい。 Examples of anionic polymerizable active metals include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanoid rare earth metals such as lanthanum and neodymium. .. Among the anionically polymerizable active metals, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
アニオン重合可能な活性金属化合物としては、有機アルカリ金属化合物が好ましい。有機アルカリ金属化合物としては、例えば、メチルリチウム、エチルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔ−ブチルリチウム、ヘキシルリチウム、フェニルリチウム、スチルベンリチウム等の有機モノリチウム化合物；ジリチオメタン、ジリチオナフタレン、１，４−ジリチオブタン、１，４−ジリチオ−２−エチルシクロヘキサン、１，３，５−トリリチオベンゼン等の多官能性有機リチウム化合物；ナトリウムナフタレン、カリウムナフタレン等が挙げられる。これら有機アルカリ金属化合物の中でも有機リチウム化合物が好ましく、有機モノリチウム化合物がより好ましい。 As the anionic polymerizable active metal compound, an organic alkali metal compound is preferable. Examples of the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; , 1,4-Dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other polyfunctional organic lithium compounds; sodium naphthalene, potassium naphthalene and the like. Among these organic alkali metal compounds, an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
有機アルカリ金属化合物の使用量は、液状ジエン系ゴム（Ｄ）の溶融粘度、分子量などに応じて適宜設定できるが、共役ジエンを含む全単量体１００質量部に対して、通常０．０１〜３質量部の量で使用される。 The amount of the organic alkali metal compound used can be appropriately set according to the melt viscosity, molecular weight, etc. of the liquid diene rubber (D), but is usually 0.01 to 100 parts by mass with respect to 100 parts by mass of all the monomers containing the conjugated diene. Used in quantities of 3 parts by mass.
上記有機アルカリ金属化合物は、ジブチルアミン、ジヘキシルアミン、ジベンジルアミンなどの第２級アミンと反応させて、有機アルカリ金属アミドとして使用することもできる。 The organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, or dibenzylamine.
極性化合物は、アニオン重合において、通常、反応を失活させず、共役ジエン部位のミクロ構造（例えば、ビニル結合量）を調整するため用いられる。極性化合物としては、例えば、ジブチルエーテル、テトラヒドロフラン、エチレングリコールジエチルエーテル等のエーテル化合物；Ｎ，Ｎ，Ｎ'，Ｎ'−テトラメチルエチレンジアミン、トリメチルアミン等の３級アミン；アルカリ金属アルコキシド、ホスフィン化合物などが挙げられる。極性化合物は、有機アルカリ金属化合物に対して、通常０．０１〜１０００モルの量で使用される。 Polar compounds are usually used in anionic polymerization to adjust the microstructure (eg, vinyl bond amount) of the conjugated diene site without inactivating the reaction. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as N, N, N', N'-tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds. Can be mentioned. The polar compound is usually used in an amount of 0.01-1000 mol with respect to the organic alkali metal compound.
溶液重合の温度は、通常−８０〜１５０℃の範囲、好ましくは０〜１００℃の範囲、より好ましくは１０〜９０℃の範囲である。重合様式は回分式あるいは連続式のいずれでもよい。 The temperature of solution polymerization is usually in the range of −80 to 150 ° C., preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 90 ° C. The polymerization mode may be either a batch type or a continuous type.
重合反応は、重合停止剤の添加により停止できる。重合停止剤としては、例えば、メタノール、イソプロパノール等のアルコールが挙げられる。得られた重合反応液をメタノール等の貧溶媒に注いで、液状ジエン系ゴム（Ｄ）を析出させるか、重合反応液を水で洗浄し、分離後、乾燥することにより上記液状ジエン系ゴム（Ｄ）を単離できる。 The polymerization reaction can be stopped by adding a polymerization inhibitor. Examples of the polymerization terminator include alcohols such as methanol and isopropanol. The obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate the liquid diene rubber (D), or the polymerization reaction solution is washed with water, separated, and dried to obtain the above liquid diene rubber (D). D) can be isolated.
上記液状ジエン系ゴム（Ｄ）の製造方法としては、上記方法の中でも、溶液重合法が好ましい。このようにして得られた液状ジエン系ゴム（Ｄ）は、そのまま未変性の状態で使用されてもよいが、その液状ジエン系ゴム中に含まれる炭素−炭素不飽和結合の少なくとも一部を水素添加された物を使用してもよい。また、液状ジエン系ゴム（Ｄ）として、変性化合物等を付加などした変性液状ジエン系ゴムを用いてもよいが、変性化合物等が付加されていない液状ジエン系ゴムを用いることが好ましい。 Among the above methods, the solution polymerization method is preferable as the method for producing the liquid diene rubber (D). The liquid diene rubber (D) thus obtained may be used as it is in an unmodified state, but at least a part of carbon-carbon unsaturated bonds contained in the liquid diene rubber is hydrogenated. An added product may be used. Further, as the liquid diene rubber (D), a modified liquid diene rubber to which a modified compound or the like is added may be used, but it is preferable to use a liquid diene rubber to which no modified compound or the like is added.
液状ジエン系ゴム（Ｄ）の重量平均分子量（Ｍｗ）は３，０００以上１２０，０００以下であり、３，０００以上８０，０００以下が好ましく、３，５００以上７５，０００以下がより好ましく、４，０００以上７０，０００以下がさらに好ましく、５，０００以上６０，０００以下がよりさらに好ましく、５，０００以上５０，０００以下が特に好ましく、５，２００以上４０，０００以下がより特に好ましい。液状ジエン系ゴム（Ｄ）のＭｗが前記範囲内であると本発明のゴム組成物の加工性が良好になり、スコーチ安定性が向上する。なお、本明細書において液状ジエン系ゴム（Ｄ）のＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した標準ポリスチレン換算の重量平均分子量である。本発明においては、Ｍｗが異なる２種以上の液状ジエン系ゴム（Ｄ）を組み合わせて用いてもよい。 The weight average molecular weight (Mw) of the liquid diene rubber (D) is 3,000 or more and 120,000 or less, preferably 3,000 or more and 80,000 or less, and more preferably 3,500 or more and 75,000 or less. More preferably 5,000 or more and 70,000 or less, further preferably 5,000 or more and 60,000 or less, particularly preferably 5,000 or more and 50,000 or less, and even more preferably 5,200 or more and 40,000 or less. When the Mw of the liquid diene rubber (D) is within the above range, the processability of the rubber composition of the present invention is improved, and the scorch stability is improved. In the present specification, Mw of the liquid diene rubber (D) is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC). In the present invention, two or more kinds of liquid diene rubbers (D) having different Mw may be used in combination.
液状ジエン系ゴム（Ｄ）の分子量分布（Ｍｗ／Ｍｎ）は１．０〜２０．０が好ましく、１．０〜１５．０がより好ましく、１．０〜１０．０がさらに好ましい。Ｍｗ／Ｍｎが前記範囲内であると、得られる液状ジエン系ゴム（Ｄ）の粘度のばらつきが小さく、より好ましい。なお、分子量分布（Ｍｗ／Ｍｎ）は、ＧＰＣの測定により求めた標準ポリスチレン換算の重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）の比を意味する。 The molecular weight distribution (Mw / Mn) of the liquid diene rubber (D) is preferably 1.0 to 20.0, more preferably 1.0 to 15.0, and even more preferably 1.0 to 10.0. When Mw / Mn is within the above range, the variation in viscosity of the obtained liquid diene rubber (D) is small, which is more preferable. The molecular weight distribution (Mw / Mn) means the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of standard polystyrene obtained by GPC measurement.
上記液状ジエン系ゴム（Ｄ）の３８℃で測定した溶融粘度は、０．１〜４，０００Ｐａ・ｓが好ましく、０．１〜３，５００Ｐａ・ｓがより好ましく、０．１〜３，０００Ｐａ・ｓがさらに好ましい。液状ジエン系ゴム（Ｄ）の溶融粘度が前記範囲内であると、得られるゴム組成物の柔軟性が向上するため、加工性が向上する。なお、本発明において液状ジエン系ゴム（Ｄ）の溶融粘度は、３８℃においてブルックフィールド型粘度計により測定した値である。 The melt viscosity of the liquid diene rubber (D) measured at 38 ° C. is preferably 0.1 to 4,000 Pa · s, more preferably 0.1 to 3,500 Pa · s, and 0.1 to 3,000 Pa · s. -S is more preferable. When the melt viscosity of the liquid diene rubber (D) is within the above range, the flexibility of the obtained rubber composition is improved, so that the workability is improved. In the present invention, the melt viscosity of the liquid diene rubber (D) is a value measured by a Brookfield type viscometer at 38 ° C.
上記液状ジエン系ゴム（Ｄ）のガラス転移温度（Ｔｇ）は、イソプレン単位、ブタジエン単位及び共役ジエン（ｄ１）単位のビニル結合量、共役ジエン（ｄ１）の種類、共役ジエン以外の単量体に由来する単位の含量などによって変化し得るが、−１５０〜５０℃が好ましく、−１３０〜５０℃がより好ましく、−１００〜５０℃がさらに好ましい。前記範囲であると、粘度が高くなるのを抑えることができ、取り扱いが容易になる。また、液状ジエン系ゴム（Ｄ）のガラス転移温度（Ｔｇ）が−１５０℃以上であると、ゴム組成物から得られる架橋物の所望の物性が向上しやすく、耐久性が良好となる傾向にある。 The glass transition temperature (Tg) of the liquid diene rubber (D) can be determined by the amount of vinyl bonds in isoprene units, butadiene units and conjugated diene (d1) units, the type of conjugated diene (d1), and a monomer other than the conjugated diene. Although it may vary depending on the content of the unit from which it is derived, it is preferably −150 to 50 ° C, more preferably −130 to 50 ° C, and even more preferably −100 to 50 ° C. Within the above range, it is possible to suppress an increase in viscosity and facilitate handling. Further, when the glass transition temperature (Tg) of the liquid diene rubber (D) is −150 ° C. or higher, the desired physical properties of the crosslinked product obtained from the rubber composition tend to be improved, and the durability tends to be improved. is there.
上記液状ジエン系ゴム（Ｄ）のビニル結合量は７０モル％以下であることが好ましく、１０〜７０モル％の範囲にあることがより好ましく、２０〜６５モル％の範囲にあることがさらに好ましい。液状ジエン系ゴム（Ｄ）のビニル結合量が上記範囲にあると、加工性、力学物性により優れ、スコーチ安定性に優れる傾向にある。液状ジエン系ゴム（Ｄ）はビニル結合量が多いほど過酸化物により架橋反応速度が高くなる。そのため、ビニル結合量が高すぎると、所望する以上の速度で架橋反応が進み、スコーチ安定性に乏しく、加工性や力学硬度に劣ったゴム組成物となる。一方、ビニル結合量が少なすぎると、液状ジエン系ゴム（Ｄ）が水素添加ニトリルゴムと架橋せず、ブリードアウトする虞がある。本発明において、「ビニル結合量」とは、液状ジエン系ゴム（Ｄ）に含まれる共役ジエン単位の合計１００モル％中、１，２−結合又は３，４−結合で結合をしている共役ジエン単位（１，４−結合以外で結合をしている共役ジエン単位）の合計モル％を意味する。ビニル結合量は、1Ｈ−ＮＭＲを用いて１，２−結合又は３，４−結合で結合をしている共役ジエン単位由来のピークと１，４−結合で結合をしている共役ジエン単位に由来するピークの面積比から算出することができる。なお、液状ジエン系ゴム（Ｄ）のビニル結合量は、例えば、液状ジエン系ゴム（Ｄ）を製造する際に使用する溶媒の種類、必要に応じて使用される極性化合物、重合温度などを制御することにより所望の値とすることができる。The vinyl bond amount of the liquid diene rubber (D) is preferably 70 mol% or less, more preferably 10 to 70 mol%, and further preferably 20 to 65 mol%. .. When the vinyl bond amount of the liquid diene rubber (D) is within the above range, the processability and mechanical characteristics tend to be excellent, and the scorch stability tends to be excellent. In the liquid diene rubber (D), the larger the vinyl bond amount, the higher the cross-linking reaction rate due to the peroxide. Therefore, if the vinyl bond amount is too high, the cross-linking reaction proceeds at a speed higher than desired, resulting in a rubber composition having poor scorch stability and poor processability and mechanical hardness. On the other hand, if the vinyl bond amount is too small, the liquid diene rubber (D) may not crosslink with the hydrogenated nitrile rubber and may bleed out. In the present invention, the "vinyl bond amount" is a conjugate having a 1,2-bond or a 3,4-bond bond in a total of 100 mol% of the conjugated diene units contained in the liquid diene rubber (D). It means the total mol% of diene units (conjugated diene units that are bonded other than 1,4-bonds). The amount of vinyl bond is the peak derived from the conjugated diene unit that is bonded by 1,2-bond or 3,4-bond using 1 H-NMR, and the conjugated diene unit that is bonded by 1,4-bond. It can be calculated from the area ratio of the peaks derived from. The vinyl bond amount of the liquid diene rubber (D) controls, for example, the type of solvent used when producing the liquid diene rubber (D), the polar compound used as necessary, the polymerization temperature, and the like. By doing so, the desired value can be obtained.
上記液状ジエン系ゴム（Ｄ）は、１種単独で用いられてもよく、２種以上を併用してもよい。
上記液状ジエン系ゴム（Ｄ）は、その製造に用いる重合触媒に由来する触媒残渣量が、金属換算で０〜２００ｐｐｍの範囲にあることが好ましい。例えば、液状ジエン系ゴム（Ｄ）を製造するための重合触媒として有機リチウム化合物等の有機アルカリ金属を用いた場合には、触媒残渣量の基準となる金属は、リチウム等のアルカリ金属になる。触媒残渣量が上記範囲にあることにより、加工等する際にタックが低下せず、また本発明のゴム組成物から得られる架橋物の耐久性が向上する。液状ジエン系ゴム（Ｄ）の製造に用いる重合触媒に由来する触媒残渣量としては、金属換算で、より好ましくは０〜１５０ｐｐｍ、さらに好ましくは０〜１００ｐｐｍである。なお、触媒残渣量は、例えば偏光ゼーマン原子吸光分光光度計を用いることにより測定できる。The liquid diene rubber (D) may be used alone or in combination of two or more.
The liquid diene rubber (D) preferably has a catalyst residue amount derived from the polymerization catalyst used for its production in the range of 0 to 200 ppm in terms of metal. For example, when an organic alkali metal such as an organic lithium compound is used as a polymerization catalyst for producing the liquid diene rubber (D), the metal that serves as a reference for the amount of catalyst residue is an alkali metal such as lithium. When the amount of the catalyst residue is in the above range, the tack does not decrease during processing and the like, and the durability of the crosslinked product obtained from the rubber composition of the present invention is improved. The amount of catalyst residue derived from the polymerization catalyst used in the production of the liquid diene rubber (D) is more preferably 0 to 150 ppm, still more preferably 0 to 100 ppm in terms of metal. The amount of catalyst residue can be measured by using, for example, a polarized Zeeman atomic absorption spectrophotometer.
液状ジエン系ゴム（Ｄ）の触媒残渣量をこのような特定の量とする方法としては、液状ジエン系ゴムを精製し、触媒残渣を十分に除去する方法などが挙げられる。精製する方法としては、水若しくは温水、又はメタノール、アセトンなどに代表される有機溶媒若しくは超臨界流体二酸化炭素による洗浄が好ましい。洗浄回数としては、経済的な観点から１〜２０回が好ましく、１〜１０回がより好ましい。また、洗浄温度としては、２０〜１００℃が好ましく、４０〜９０℃がより好ましい。また重合反応前に、重合の阻害を行うような不純物を蒸留や吸着剤により除去し、単量体の純度を高めた後に重合を行うことによっても、必要な重合触媒量が少なくてすむため、触媒残渣量を低減することができる。また、上記と同様の観点から、本発明のゴム組成物中の触媒残渣量が、金属換算で０〜２００ｐｐｍであることが好ましく、０〜１５０ｐｐｍがより好ましく、０〜１００ｐｐｍがさらに好ましい。この場合の触媒残渣量は水素添加ニトリルゴム（Ａ）、液状ジエン系ゴム（Ｄ）及び／又は該ゴム組成物中に含まれるその他任意成分の製造に用いる重合触媒に由来する触媒残渣量であってもよい。 Examples of the method for setting the amount of the catalyst residue of the liquid diene rubber (D) to such a specific amount include a method of purifying the liquid diene rubber and sufficiently removing the catalyst residue. As a method for purification, washing with water or warm water, an organic solvent typified by methanol, acetone, or supercritical fluid carbon dioxide is preferable. From an economical point of view, the number of washings is preferably 1 to 20 times, more preferably 1 to 10 times. The cleaning temperature is preferably 20 to 100 ° C, more preferably 40 to 90 ° C. In addition, the amount of polymerization catalyst required can be reduced by removing impurities that inhibit polymerization by distillation or an adsorbent before the polymerization reaction to increase the purity of the monomer and then performing polymerization. The amount of catalyst residue can be reduced. From the same viewpoint as above, the amount of catalyst residue in the rubber composition of the present invention is preferably 0 to 200 ppm, more preferably 0 to 150 ppm, and even more preferably 0 to 100 ppm in terms of metal. In this case, the amount of catalyst residue is the amount of catalyst residue derived from the polymerization catalyst used for producing the hydrogenated nitrile rubber (A), the liquid diene rubber (D) and / or other optional components contained in the rubber composition. You may.
本発明のゴム組成物において、水素添加ニトリルゴム（Ａ）１００質量部に対する液状ジエン系ゴム（Ｄ）の含有量は、１〜２０質量部であり、３〜１５質量部が好ましく、３〜８質量部がより好ましい。液状ジエン系ゴム（Ｄ）の含有量が上記範囲内であると、ゴム組成物の加工性が良好になり、スコーチ安定性も向上する。 In the rubber composition of the present invention, the content of the liquid diene rubber (D) with respect to 100 parts by mass of the hydrogenated nitrile rubber (A) is 1 to 20 parts by mass, preferably 3 to 15 parts by mass, and 3 to 8 parts by mass. Parts by mass are more preferred. When the content of the liquid diene rubber (D) is within the above range, the processability of the rubber composition is improved and the scorch stability is also improved.
本発明のゴム組成物は、本発明の効果を阻害しない範囲で、加工性、流動性等の改良を目的とし、必要に応じてシリコンオイル、アロマオイル、ＴＤＡＥ（Ｔｒｅａｔｅｄ Ｄｉｓｔｉｌｌｅｄ Ａｒｏｍａｔｉｃ Ｅｘｔｒａｃｔｓ）、ＭＥＳ（Ｍｉｌｄ Ｅｘｔｒａｃｔｅｄ Ｓｏｌｖａｔｅｓ）、ＲＡＥ（Ｒｅｓｉｄｕａｌ Ａｒｏｍａｔｉｃ Ｅｘｔｒａｃｔｓ）、パラフィンオイル、ナフテンオイル等のプロセスオイル、フタレート系可塑剤、セバケート系可塑剤、アジペート系可塑剤等のエステルオイル、脂肪族炭化水素樹脂、脂環族炭化水素樹脂、Ｃ９系樹脂、ロジン系樹脂、クマロン・インデン系樹脂、フェノール系樹脂等の樹脂成分を軟化剤として含有していてもよい。本発明のゴム組成物が上記プロセスオイルを軟化剤として含有する場合には、その含有量は、水素添加ニトリルゴム（Ａ）１００質量部に対して５０質量部より少ないことが好ましい。一方、本発明のゴム組成物では、可塑剤を含まないことも本発明の好ましい一態様である。可塑剤は一般に分子量が小さく、ブリードアウトの虞があるが、本発明においては、液状ジエン系ゴム（Ｄ）が混練時に可塑剤としての役割を担う。また、本発明の液状ジエン系ゴム（Ｄ）は、水素添加ニトリルゴムと架橋構造を形成できるため、ブリードアウトの虞が無い。 The rubber composition of the present invention aims to improve processability, fluidity, etc. within a range that does not impair the effects of the present invention, and if necessary, silicon oil, aroma oil, TDAE (Treated Plasticized Aromatic Industries), MES ( Mild Extracted Solves), RAE (Residal Aromatic Elements), paraffin oil, naphthenic oil and other process oils, phthalate plasticizers, sebacate plasticizers, adipate plasticizers and other ester oils, aliphatic hydrocarbon resins, alicyclics. A resin component such as a hydrocarbon resin, a C9 resin, a rosin resin, a kumaron / inden resin, or a phenol resin may be contained as a softening agent. When the rubber composition of the present invention contains the process oil as a softener, the content thereof is preferably less than 50 parts by mass with respect to 100 parts by mass of the hydrogenated nitrile rubber (A). On the other hand, it is also a preferable aspect of the present invention that the rubber composition of the present invention does not contain a plasticizer. The plasticizer generally has a small molecular weight and may bleed out. However, in the present invention, the liquid diene rubber (D) plays a role as a plasticizer during kneading. Further, since the liquid diene rubber (D) of the present invention can form a crosslinked structure with the hydrogenated nitrile rubber, there is no risk of bleeding out.
本発明のゴム組成物は、本発明の効果を阻害しない範囲で、耐候性、耐熱性、耐酸化性等の向上を目的として、必要に応じて老化防止剤、ワックス、酸化防止剤、滑剤、光安定剤、スコーチ防止剤、加工助剤、顔料や色素等の着色剤、難燃剤、帯電防止剤、艶消し剤、ブロッキング防止剤、紫外線吸収剤、離型剤、発泡剤、抗菌剤、防カビ剤、香料等の添加剤を含有してもよい。酸化防止剤としては、例えば、ヒンダードフェノール系化合物、リン系化合物、ラクトン系化合物、ヒドロキシル系化合物等が挙げられる。老化防止剤としては、例えば、アミン−ケトン系化合物、イミダゾール系化合物、アミン系化合物、フェノール系化合物、硫黄系化合物及びリン系化合物等が挙げられる。これら添加剤は、１種単独で用いられてもよく、２種以上を併用してもよい。
また本発明のゴム組成物は、本発明の効果を損なわない範囲で、水素添加ニトリルゴム（Ａ）以外の固形ゴムを含んでいてもよい。The rubber composition of the present invention contains antistatic agents, waxes, antioxidants, lubricants, etc., as necessary, for the purpose of improving weather resistance, heat resistance, oxidation resistance, etc., as long as the effects of the present invention are not impaired. Light stabilizers, scorch inhibitors, processing aids, colorants such as pigments and pigments, flame retardants, antistatic agents, matting agents, blocking inhibitors, UV absorbers, mold release agents, foaming agents, antibacterial agents, antibacterial agents It may contain additives such as fungicides and fragrances. Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds and the like. Examples of the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds and phosphorus compounds. These additives may be used alone or in combination of two or more.
Further, the rubber composition of the present invention may contain a solid rubber other than the hydrogenated nitrile rubber (A) as long as the effects of the present invention are not impaired.
［ゴム組成物の製造方法］
本発明のゴム組成物の製造方法は、上記各成分を均一に混合できれば特に限定されない。ゴム組成物の製造に用いる装置としては、例えば、ニーダールーダー、ブラベンダー、バンバリーミキサー、インターナルミキサー等の接線式又は噛合式の密閉式混練機、単軸押出機、二軸押出機、ミキシングロール、及びローラーなどが挙げられる。上記ゴム組成物を製造は、通常７０〜２７０℃の温度範囲で行うことができる。[Manufacturing method of rubber composition]
The method for producing the rubber composition of the present invention is not particularly limited as long as each of the above components can be uniformly mixed. Equipment used for manufacturing the rubber composition includes, for example, a tangential or meshing closed kneader such as a kneader luder, a lavender, a Banbury mixer, an internal mixer, a single-screw extruder, a twin-screw extruder, and a mixing roll. , And rollers. The rubber composition can usually be produced in a temperature range of 70 to 270 ° C.
［架橋物］
本発明のゴム組成物を架橋することにより、架橋物を得ることができる。ゴム組成物の架橋条件は、その用途等に応じて適宜設定できる。[Crosslinked product]
By cross-linking the rubber composition of the present invention, a cross-linked product can be obtained. The cross-linking conditions of the rubber composition can be appropriately set according to the application and the like.
有機過酸化物を架橋剤とし、ゴム組成物を金型により架橋する場合には、架橋温度は通常１００〜２００℃、加圧条件は通常０．５〜２．０ＭＰａとし、架橋することができる。 When the organic peroxide is used as a cross-linking agent and the rubber composition is cross-linked by a mold, the cross-linking temperature is usually 100 to 200 ° C. and the pressurizing condition is usually 0.5 to 2.0 MPa. ..
本発明のゴム組成物は、水素添加ニトリルゴムの優れた特性を損なうことなく、加工性、スコーチ安定性に優れるため、種々の用途に用いることができる。
本発明のゴム組成物から得られる架橋物は、例えば、ガスケット、Ｏ−リング、オイルシール、ホース、ベルトなど種々の用途に好適に用いられる。The rubber composition of the present invention can be used for various purposes because it is excellent in processability and scorch stability without impairing the excellent properties of the hydrogenated nitrile rubber.
The crosslinked product obtained from the rubber composition of the present invention is suitably used for various applications such as gaskets, O-rings, oil seals, hoses, and belts.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
本実施例及び比較例において使用した各成分は以下のとおりである。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The components used in this example and the comparative example are as follows.
＜水素添加ニトリルゴム（Ａ）＞
ゼットポール２０２０（日本ゼオン株式会社製）
（アクリロニトリル単位の含有量３６．２％、ヨウ素価２８、ムーニー粘度７８）
＜フィラー（Ｂ）＞
カーボンブラック：シーストＧ−ＳＯ（東海カーボン株式会社製）
＜有機過酸化物（Ｃ）＞
パーブチルＰ（日油株式会社製）
＜液状ジエン系ゴム（Ｄ）＞
後述の製造例１〜５で得られた液状ジエン系ゴム
＜任意成分＞
架橋助剤：アクリルエステルＴＭＰ（三菱ケミカル株式会社製）
可塑剤：ＢＡＸ−Ｒ（大八化学工業株式会社製）
老化防止剤：ノクラック２２４（大内新興化学工業株式会社製）<Hydrogenated nitrile rubber (A)>
Z-Pole 2020 (manufactured by Zeon Corporation)
(Content of acrylonitrile unit 36.2%, iodine value 28, Mooney viscosity 78)
<Filler (B)>
Carbon Black: Seest G-SO (manufactured by Tokai Carbon Co., Ltd.)
<Organic peroxide (C)>
Perbutyl P (manufactured by NOF CORPORATION)
<Liquid diene rubber (D)>
Liquid diene rubber obtained in Production Examples 1 to 5 described later <optional component>
Crosslinking aid: Acrylic ester TMP (manufactured by Mitsubishi Chemical Corporation)
Plasticizer: BAX-R (manufactured by Daihachi Chemical Industry Co., Ltd.)
Anti-aging agent: Nocrack 224 (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
製造例１：液状ジエン系ゴム（Ｄ−１）の製造
十分に乾燥した５Ｌオートクレーブを窒素置換し、ヘキサン１１００ｇ及びｎ−ブチルリチウム（１７質量％ヘキサン溶液）２０４ｇを仕込み、５０℃に昇温した後、撹拌条件下、重合温度を５０℃となるように制御しながら、Ｎ,Ｎ,Ｎ',Ｎ'−テトラメチルエチレンジアミン１０ｇと、ブタジエン１３００ｇを逐次添加して、１時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を７０℃で２４時間真空乾燥することにより、液状ジエン系ゴム（Ｄ−１）を得た。得られた液状ジエン系ゴム（Ｄ−１）の物性を表１に示す。Production Example 1: Production of liquid diene rubber (D-1) A sufficiently dried 5 L autoclave was substituted with nitrogen, 1100 g of hexane and 204 g of n-butyllithium (17 mass% hexane solution) were charged, and the temperature was raised to 50 ° C. Then, under stirring conditions, while controlling the polymerization temperature to be 50 ° C., 10 g of N, N, N', N'-tetramethylethylenediamine and 1300 g of butadiene were sequentially added and polymerized for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum-dried at 70 ° C. for 24 hours to obtain a liquid diene rubber (D-1). Table 1 shows the physical characteristics of the obtained liquid diene rubber (D-1).
製造例２：液状ジエン系ゴム（Ｄ−２）の製造
十分に乾燥した５Ｌオートクレーブを窒素置換し、ヘキサン１１００ｇ及びｎ−ブチルリチウム（１７質量％ヘキサン溶液）３３ｇを仕込み、５０℃に昇温した後、撹拌条件下、重合温度を５０℃となるように制御しながら、Ｎ,Ｎ,Ｎ',Ｎ'−テトラメチルエチレンジアミン２．２ｇと、ブタジエン１３２０ｇを逐次添加して、１時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を７０℃で２４時間真空乾燥することにより、液状ジエン系ゴム（Ｄ−２）を得た。得られた液状ジエン系ゴム（Ｄ−２）の物性を表１に示す。Production Example 2: Production of liquid diene rubber (D-2) A sufficiently dried 5 L autoclave was substituted with nitrogen, 1100 g of hexane and 33 g of n-butyllithium (17 mass% hexane solution) were charged, and the temperature was raised to 50 ° C. Then, under stirring conditions, while controlling the polymerization temperature to be 50 ° C., 2.2 g of N, N, N', N'-tetramethylethylenediamine and 1320 g of butadiene were sequentially added and polymerized for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain a liquid diene rubber (D-2). Table 1 shows the physical characteristics of the obtained liquid diene rubber (D-2).
製造例３：液状ジエン系ゴム（Ｄ−３）の製造
十分に乾燥した５Ｌオートクレーブを窒素置換し、ヘキサン１１００ｇ及びｎ−ブチルリチウム（１７質量％ヘキサン溶液）２０４ｇを仕込み、５０℃に昇温した後、撹拌条件下、重合温度を５０℃となるように制御しながら、ブタジエン１３００ｇを逐次添加して、１時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を７０℃で２４時間真空乾燥することにより、液状ジエン系ゴム（Ｄ−３）を得た。得られた液状ジエン系ゴム（Ｄ−３）の物性を表１に示す。Production Example 3: Production of liquid diene rubber (D-3) A sufficiently dried 5 L autoclave was substituted with nitrogen, 1100 g of hexane and 204 g of n-butyllithium (17 mass% hexane solution) were charged, and the temperature was raised to 50 ° C. Then, under stirring conditions, 1300 g of butadiene was sequentially added while controlling the polymerization temperature to be 50 ° C., and the polymerization was carried out for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain a liquid diene rubber (D-3). Table 1 shows the physical characteristics of the obtained liquid diene rubber (D-3).
製造例４：液状ジエン系ゴム（Ｄ−４）の製造
十分に乾燥した５Ｌオートクレーブを窒素置換し、シクロヘキサン１２８０ｇ及びｓ−ブチルリチウム（１０．５質量％シクロヘキサン溶液）２０４ｇを仕込み、５０℃に昇温した後、撹拌条件下、重合温度を５０℃となるように制御しながら、ブタジエン１３５０ｇを逐次添加して、１時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を７０℃で２４時間真空乾燥することにより、液状ジエン系ゴム（Ｄ−４）を得た。得られた液状ジエン系ゴム（Ｄ−４）の物性を表１に示す。Production Example 4: Production of liquid diene rubber (D-4) A sufficiently dried 5 L autoclave is substituted with nitrogen, 1280 g of cyclohexane and 204 g of s-butyllithium (10.5 mass% cyclohexane solution) are charged, and the temperature is raised to 50 ° C. After warming, 1350 g of butadiene was sequentially added under stirring conditions while controlling the polymerization temperature to be 50 ° C., and polymerization was carried out for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain a liquid diene rubber (D-4). Table 1 shows the physical characteristics of the obtained liquid diene rubber (D-4).
製造例５：液状ジエン系ゴム（Ｄ−５）の製造
十分に乾燥した５Ｌオートクレーブを窒素置換し、シクロヘキサン１１００ｇ及びｓ−ブチルリチウム（１０．５質量％シクロヘキサン溶液）５４ｇを仕込み、５０℃に昇温した後、撹拌条件下、重合温度を５０℃となるように制御しながら、Ｎ,Ｎ,Ｎ',Ｎ'−テトラメチルエチレンジアミン５．１ｇと、予め調製したブタジエン、スチレンの混合物（ブタジエン３６０ｇとスチレン９０ｇをボンベ内で混合）４５０ｇを逐次添加して、１時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を７０℃で２４時間真空乾燥することにより、液状ジエン系ゴム（Ｄ−５）を得た。得られた液状ジエン系ゴム（Ｄ−５）の物性を表１に示す。
なお、製造例で得られた液状ジエン系ゴムの各物性の測定方法及び算出方法は以下の通りである。Production Example 5: Production of liquid diene rubber (D-5) A sufficiently dried 5L autoclave is substituted with nitrogen, 1100 g of cyclohexane and 54 g of s-butyllithium (10.5 mass% cyclohexane solution) are charged, and the temperature is raised to 50 ° C. After warming, under stirring conditions, while controlling the polymerization temperature to 50 ° C., 5.1 g of N, N, N', N'-tetramethylethylenediene and a pre-prepared mixture of butadiene and styrene (360 g of butadiene). And 90 g of styrene were mixed in a bomb) 450 g was sequentially added and polymerized for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain a liquid diene rubber (D-5). Table 1 shows the physical characteristics of the obtained liquid diene rubber (D-5).
The methods for measuring and calculating the physical properties of the liquid diene rubber obtained in the production example are as follows.
（重量平均分子量の測定方法）
液状ジエン系ゴム（Ｄ）の重量平均分子量は、ＧＰＣにより標準ポリスチレン換算分子量で求めた。測定装置及び条件は、以下の通りである。
・装置 ：東ソー株式会社製ＧＰＣ装置「ＧＰＣ８０２０」
・分離カラム ：東ソー株式会社製「ＴＳＫｇｅｌＧ４０００ＨＸＬ」
・検出器 ：東ソー株式会社製「ＲＩ−８０２０」
・溶離液 ：テトラヒドロフラン
・溶離液流量 ：１．０ｍＬ／分
・サンプル濃度：５ｍｇ／１０ｍＬ
・カラム温度 ：４０℃(Measurement method of weight average molecular weight)
The weight average molecular weight of the liquid diene rubber (D) was determined by GPC in terms of standard polystyrene equivalent molecular weight. The measuring device and conditions are as follows.
-Device: GPC device "GPC8020" manufactured by Tosoh Corporation
-Separation column: "TSKgelG4000HXL" manufactured by Tosoh Corporation
-Detector: "RI-8020" manufactured by Tosoh Corporation
-Eluent: tetrahydrofuran-Eluent flow rate: 1.0 mL / min-Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C
（ビニル結合量）
液状ジエン系ゴム（Ｄ）のビニル結合量を、日本電子株式会社製1Ｈ−ＮＭＲ（５００ＭＨｚ）を使用し、サンプル／重クロロホルム＝５０ｍｇ／１ｍＬの濃度、積算回数１０２４回で測定した。得られたスペクトルのビニル化されたジエン化合物由来の二重結合のピークと、ビニル化されていないジエン化合物由来の二重結合のピークとの面積比から、ビニル結合量を算出した。(Amount of vinyl bond)
The vinyl bond amount of the liquid diene rubber (D) was measured using 1 H-NMR (500 MHz) manufactured by JEOL Ltd. at a concentration of sample / deuterated chloroform = 50 mg / 1 mL and an integration number of 1024 times. The amount of vinyl bond was calculated from the area ratio of the peak of the double bond derived from the vinylized diene compound and the peak of the double bond derived from the non-vinylized diene compound in the obtained spectrum.
（ガラス転移温度）
液状ジエン系ゴム（Ｄ）１０ｍｇをアルミパンに採取し、示差走査熱量測定（ＤＳＣ）により１０℃／分の昇温速度条件においてサーモグラムを測定し、ＤＤＳＣのピークトップの値をガラス転移温度とした。(Glass-transition temperature)
10 mg of liquid diene rubber (D) was sampled in an aluminum pan, and the thermogram was measured under differential scanning calorimetry (DSC) at a temperature rise rate of 10 ° C./min, and the peak top value of DDSC was defined as the glass transition temperature. did.
（３８℃における溶融粘度の測定方法）
液状ジエン系ゴム（Ｄ）の３８℃における溶融粘度をブルックフィールド型粘度計（ＢＲＯＯＫＦＩＥＬＤ ＥＮＧＩＮＥＥＲＩＮＧ ＬＡＢＳ. ＩＮＣ.製）により測定した。(Measurement method of melt viscosity at 38 ° C)
The melt viscosity of the liquid diene rubber (D) at 38 ° C. was measured with a Brookfield viscometer (BROOKFIELD ENGINEERING LABS. INC.).
実施例１〜６及び比較例１、２
表２に記載した配合割合（質量部）にしたがって、水素添加ニトリルゴム（Ａ）、フィラー（Ｂ）、有機過酸化物（Ｃ）、液状ジエン系ゴム（Ｄ）、架橋助剤、可塑剤、及び老化防止剤を、オープンロールを用いて混練し、未架橋ゴムシートを得た。得られた未架橋ゴムシートを用いて、ムーニー粘度、スコーチ時間ｔ5、９０％架橋時間ｔc（９０）を、下記の方法に基づき、それぞれ評価した。結果を表２に示す。Examples 1 to 6 and Comparative Examples 1 and 2
Hydrogenated nitrile rubber (A), filler (B), organic peroxide (C), liquid diene rubber (D), cross-linking aid, plasticizer, according to the compounding ratio (parts by mass) shown in Table 2. And the anti-aging agent were kneaded using an open roll to obtain an uncrosslinked rubber sheet. Using the obtained uncrosslinked rubber sheet, Mooney viscosity, scorch time t 5 , and 90% cross-linking time t c (90) were evaluated based on the following methods, respectively. The results are shown in Table 2.
得られた未架橋ゴムシートをプレス成形（１８０℃、７分）して架橋ゴムシート（厚み２ｍｍ）を作製し、下記の方法に基づき、硬度、引張強さ、切断時伸びを評価した。結果を表２に示す。 The obtained uncrosslinked rubber sheet was press-molded (180 ° C., 7 minutes) to prepare a crosslinked rubber sheet (thickness 2 mm), and the hardness, tensile strength, and elongation at cutting were evaluated based on the following methods. The results are shown in Table 2.
なお、各評価の測定方法は以下のとおりである。
（ムーニー粘度ＭＬ1+4，１００℃）
実施例及び比較例で作製した未架橋ゴムシートを用い、ＪＩＳ Ｋ ６３００に準拠し、Ｌ形ロータを使用して、予熱１分、ロータ作動時間４分、温度１００℃の条件で求めた。The measurement method for each evaluation is as follows.
(Moony viscosity ML 1 + 4 , 100 ° C)
Using the uncrosslinked rubber sheets prepared in Examples and Comparative Examples, the results were obtained under the conditions of preheating 1 minute, rotor operating time 4 minutes, and temperature 100 ° C. using an L-shaped rotor in accordance with JIS K 6300.
（ムーニースコーチ時間ｔ5）
実施例及び比較例で作製した未架橋ゴムシートを用い、ＪＩＳ Ｋ ６３００に準拠し、１２５℃におけるムーニースコーチ時間ｔ5（分）を測定した。(Moonies coach time t 5 )
Using the uncrosslinked rubber sheets prepared in Examples and Comparative Examples, the Mooney scorch time t 5 (minutes) at 125 ° C. was measured according to JIS K 6300.
（９０％架橋時間ｔc（９０））
実施例及び比較例で作製した未架橋ゴムシートを用い、ＪＩＳ Ｋ ６３００に準拠し、１７０℃における９０％架橋時間ｔc（９０）（分）を測定した。(90% cross-linking time t c (90))
Using the uncrosslinked rubber sheets prepared in Examples and Comparative Examples, 90% crosslink time t c (90) (minutes) at 170 ° C. was measured according to JIS K 6300.
（硬度）
ＪＩＳ Ｋ ６２５３に準拠して、タイプＡ硬度計により、得られた架橋ゴムシートの硬度を測定した。各実施例及び比較例の数値は、表２の比較例１の値を１００とした際の相対値である。(hardness)
The hardness of the obtained crosslinked rubber sheet was measured with a Type A hardness tester according to JIS K 6253. The numerical values of each Example and Comparative Example are relative values when the value of Comparative Example 1 in Table 2 is set to 100.
（引張強さ、切断時伸び）
得られた架橋ゴムシートからダンベル状試験片を打ち抜き、インストロン社製引張試験機を用いて、ＪＩＳ Ｋ ６２５１に準じて引張強さ、切断時伸びを測定した。各実施例及び比較例の数値は、表２の比較例１の値を１００とした際の相対値である。(Tensile strength, elongation at cutting)
A dumbbell-shaped test piece was punched out from the obtained crosslinked rubber sheet, and the tensile strength and elongation at the time of cutting were measured according to JIS K 6251 using a tensile tester manufactured by Instron. The numerical values of each Example and Comparative Example are relative values when the value of Comparative Example 1 in Table 2 is set to 100.
表２より実施例１〜６のゴム組成物は９０％架橋時間が同等で、スコーチ安定性に優れることがわかる。また硬度、引張強さ、切断時伸びも高いレベルで備える。 From Table 2, it can be seen that the rubber compositions of Examples 1 to 6 have the same 90% cross-linking time and are excellent in scorch stability. It also has a high level of hardness, tensile strength, and elongation during cutting.
本発明のゴム組成物は加工性、スコーチ安定性に優れ、しかも水素添加ニトリルゴムの有する優れた特性を損なうことがない。そのため、種々の工業用部材用途などに好適に用いることができる。 The rubber composition of the present invention is excellent in processability and scorch stability, and does not impair the excellent properties of the hydrogenated nitrile rubber. Therefore, it can be suitably used for various industrial member applications.
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| CA3104093A1 (en) | 2020-01-02 |
| KR102654433B1 (en) | 2024-04-03 |
| WO2020004243A1 (en) | 2020-01-02 |
| US20210139679A1 (en) | 2021-05-13 |
| EP3816223A4 (en) | 2022-03-16 |
| TWI833772B (en) | 2024-03-01 |
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